Condensation product and textile material softened therewith



March 12, 1957 A. HIESTAND ET AL 2,785,092

CONDENSATION PRODUCT AND TEXTILE MATERIAL SOFTENED THEREWITH Filed Aug.2, 1954 INVENTdRs ARMIN HIESTAND 0nd 'OTTO ALBRECHT BY 71 M, Mfr-1%ATTORNEY 5 United States Patent G CONDENSATION PRGDUQT AND TEXTILE MATE-RIAL SOF'IENED Tl-EREWETH Armin Hiestand, Binningen, and Otto Albrecht,Neuewelt, near Basel, Switzerland, assignors to Iiba Limited, Basel,Switzerland Application August 2, 1954, Serial No. 447,443

Claims priority, application Switzerland August 11, 1953 14 Claims. (Cl.117-1395) According to this invention new condensation products are madeby reacting one molecular proportion of a polyalkylene polyamine with atleast two molecular proportions of a non-aromatic carboxylic acid with ahydrocarbon radical of high molecular weight or a functional derivativeof such acid and with at least one molecular proportion of acrylonitrileor methacrylonitrile or acrylic acid amide or methacrylic acid amide,which may, if desired, be substituted, or the corresponding fi-halogenpropionic acid derivatives. The condensation products in the form oftheir water soluble salts, including their quaternary ammonium salts,are valuable textile assistants. They are especially suitable forproducing a soft feel on the most varying types of fibers such aspolyacrylonitrile fibers, viscose rayon, polyester fibers, cuprammoniumrayon (Bemberg).

The polyamines used as starting materials for preparing the products ofthe invention should contain, apart from the hydrocarbon residues andthe basic nitrogen atoms, no further substituents. There may be used,for example, diethylene triamine, dipropylene triamine, triethylenetetramine or tetraethylene pentamine, and also polyarnines such as areobtainable by heating an ethylene dihalide with ammonia or an amine.

As non-aromatic carboxylic acids, which can be used for making thecondensation products, there may be mentioned: Caprylic acid, lauricacid, palmitic acid, stearic acid, oleic acid, linoleic acid and alsohardened train oil fatty acid or resin acids, such as abietic acid andnaphthenic acids. As functional derivatives of such acids, there comeinto consideration their halides, esters or anhydrides. These acids andtheir derivatives contain a hydrocarbon radical of high molecularweight, i. e. one of about 8 to about 40 carbon atoms. Especiallysuitable acids are those containing an aliphatic radical of 12-18 carbonatoms. a

The condensation products may be made by first reacting the polyalkylenepolyamine with the carboxylic acid or functional derivative thereof, andthen additively combining the product with acrylonitrile,methacrylonitrile or acrylic acid amide. Alternatively, the polyalkylenepolyamine may first be additively combined with acrylonitrile,methacrylonitrile or acrylic acid amide, and then reacted with thecarboxylic acid. Instead of carrying out the reaction with the acrylicacid derivatives there may also be used ,B-halogen propionic acidderivatives, for example, ,B-chloro-propionic acid nitrile, wherebywater-soluble salts of the condensation products are formed direct. Thereaction between the amine and the carboxylic acid or functionalderivative thereof may be carried out under the conditions usual forsuch reactions.

r 2,785,092 Patented Mar. 12, 1957 Similarly, for carrying out theadditive combination with acrylic acid derivatives or methacrylic acidderivatives, there may be used the conditions known for additivelycombining these compounds with amines.

For salt formation there may be used inorganic or organic acids such,for example, as hydrochloric acid, sulfuric acid, methyl-sulfuric acid,acetic acid, lactic acid or formic acid. There may also be used for saltformation organic compounds which are capable of reacting with amines,to form salts, including quaternary ammonium salts. Such compounds are,for example, benzyl chloride or dimethyl sulfate. When pasted with waterthe salts form stable pastes which can be easily dissolved in treatmentbaths to be used in accordance with the invention.

Especially valuable products are obtained by starting from diethylenetriamine and stearic acid. There may be mentioned for example, theacetate of the condensation product obtained by additively combining 1molecular proportion of acrylonitrile with 1 molecular proportion ofdiethylene triamine and then condensing with 2 molecular proportions ofcommercial stearic acid, or the quaternary ammonium salt obtained bycondensing 1 molecular proportion of diethylene triamine with 2molecular proportions of comercial stearic acid, then additivelycombining with acrylonitrile and quaternating with benzyl chloride.

The production of a soft feel on the various fibers is carried out in asimple manner by impregnating the textile fibers in an aqueous bathcontaining a salt of a product described above at ordinary or a slightlyraised temperature.

- As polyacrylonitrile fibers, of which the feel is improved inaccordance with the invention, there come into considerationhomo-polymers and co-polymers, which advantageously contain at leastpercent of polyacrylonitrile and if desired, other additions whichenhance the basic character of the polymer or its solubility. Asexamples there may be mentioned the materials known in commerce underthe names Orlon such as Orlon 81 and Orlon 41, and also Acrylan andDynel.

The accompanying sheet of drawing diagrammatically illustrates textilematerial to which a soft feel has been imparted by impregnation with apolyalkylene polyamine/non-aromatic carboxylic acid/acrylonitrile (oracrylic acid amide) condensation product according to the presentinvention.

The following examples illustrate the invention, the parts being byweight unless otherwise stated, and the relationship of parts by weightto parts by volume being the same as that of the kilogram to the liter:

Example 1 13.25 parts of acrylonitrile (one-quarter mol) are addeddropwise to 26 parts of diethylene triamine (onequarter mol) whilecooling with water. The slightly warm mixture is then heated for onehour at 65-70" C., while stirring. The acrylonitrile additively combinescompletely with the diethylene triamine.

parts of commercial stearic acid (one half mol) are then added, and thewhole is heated in an atmosphere of nitrogen at -165 C., while stirringdepending on the amount of foaming, water vapor being evolved from thereaction mixture. After heating the mixture for 4-5 The melt of thebasic condensation product from diethylene triamine, acrylonitrile andstearic acid, prepared as describedin the second paragraph of Example 1,is cooled to about 120125 C., and then 32.5 parts of freshly distilledbenzyl chloride are added. After stirring the reaction mixture for 2-3hours and heating it to 120 C., a test portion of the mixture dissolvescompletely in water with warming.

The excess of benzyl chloride is then expelled in vacuo. To theresulting melt there are cautiously run in 600 parts of Water at 70-80C., while stirring or kneading the gelatinous mass which is immediatelyformed. The mass is kneaded at 8090 C. until a fine homogeneous 'pasteis obtained.

' Instead of stearic acid, there may be used for preparing thecondensation product a corresponding quantity of oleic acid, coconut oilfatty acids or a mixture thereof.

Example 3 A product similar to that described in Example 2 is obtainedby using 30 parts of chloracetamide instead of 32.5 parts of benzylchloride. The reaction conditions are the same, but it is of greatadvantage to add during the reaction 34 parts of a mixture of equalparts of dioxane and xylene. If it is desired to obtain a cleartreatment bath, the mixture of solvents must be removed before thepasting operation in 'vacuo.

Example 4 The melt of the basic condensation product prepared asdescribed in the second paragraph of Example 1 is stirred for one houron a boiling water bath with 32.5 parts'of freshly distilled neutraldimethyl sulfate.

After adding 600 parts of water. at 6070 0, there 'is obtained a veryfine homogeneous suspension which, when freshly prepared, dissolves veryeasily in cold water.

Example 5 17.75 parts of acrylic acid amide mol) are 'dissolved withslight Warming in 26 parts of diethylene triamine A mol). After theaddition of 135 parts of stearic acid /2 mol), the mixture is slowlyheated, While stirring to 160-165 C. After heating the mixture for 4-5hours a test portion is soluble in warm dilute acetic acid.

Into 10 parts of the above melt are run on a boiling water bath 34 partsof hot acetic acid of 6.2 percent strength. There is obtained a finehomogeneous paste which can be diluted easily with hot water.

Example 6 1 26.5 parts mol) of acrylonitrile are added dropwise to 36.5.parts of triethylene tetramine 'mol), While cooling with water. 7Afterheating the mixture for one hour at 65*70" C., While-stirring,there are added 135 parts of commercial stearic acid 0/: mol) and theWhole is heated to l60l65 C. in an atmosphere of nitrogen. V V

After reaching a reaction temperature above 100 C. the mixture is heatedfor 4 5 hours, and then a test portion dissolves-clearly in warm diluteacetic acid.

By proceeding in the manner described in Example 2, there is obtainedwith 32.5 parts of benzyl chloride a water-soluble wax-like product.

If, instead of proceeding as described in the preceding paragraph, theproceduce described in Example 3 is i H n a 4 P p followed, there isobtained with chloracetamide, a watersoluble reaction product.

Example 7 The procedure is the same as described in Example 6, exceptthat 202.5 parts mol) of commercial stearic acid are used instead ofparts. During this condensation a small amount of acrylonitrile isevolved from the reaction melt.

The wax-like substance so obtained is soluble in dilute warm aceticacid.

The product can be converted as described in Example 2 with benzylchloride or as described in Example 3 with chloracetamide into thecorresponding water-soluble reaction product.

Example 8 108 parts of hardened sperm oil are added to the base preparedas described in the second paragraph of Example 1, and the mixture isheated for an hour at l90 C., and the melt is maintained, whilestirring, in an atmosphere of nitrogen for 5 hours at 185-195 C.

The product, which is wax-like at room temperature, can be convertedwith benzyl chloride as described in Example 2 into a very fine softpaste, which yields an opalescent solution when diluted with hot water.

Instead of hardened sperm oil there may be used in this example, 106.5parts of coconut oil, whereby a soft wax-like substance is obtainedwhich dissolves cornpletely to give a clear solution in dilute, aceticacid.

Instead of hardened sperm oil there may be used in this example, amixture of 54 parts of hardened sperm oil and 67.5 parts of commercialstearic acid. The product obtained in this manner dissolves somewhatmore clearly in dilute acetic acid than when hardened sperm oil alone isused. Example, 9 The condensation of" the addition product from A mol totriethylene tetramine and /2 mol of acrylonitrile with /2 mol of stearicacid as described in Example 6 is carried out in the presence of 500parts by volume of boiling' xylene. The water of condensation is removedfrom the reaction mixture by azeotropic distillation and separated fromthe xylene also carried over in a water separator, the xylene beingallowed to run back into the flask. After distilling for 24 hours 8.6 to8.8 parts of water are obtained. After distilling for a further 8 hoursno appreciable splitting off of water takes place. Accordingly, '1 molof water is split off per mol of fatty acid. p

The wax-like mass obtained after distilling off the xylene in vacuo andcooling the mixture, is of a somewhat darker color than that prepared inExample 6, but it dissolves equally well in warm dilute acetic acid.There is obtained an acetic acid paste capable of being diluted withwater by working up as described in the last paragraph of Example 1, orwater-soluble pastes are obtained by working up as described in Examples2 and 3 which contain reaction products with benzyl chloride andchloracetamide, respectively.

Example 10 113 parts of the basic condensation product from 1 mol ofdiethylene triamine and 2, mols of commercial stearic acid, which stillcontains 1 hydrogen atom bound .to a secondary nitrogen atom, aredissolved in 100 parts of benzene while warming, and 10 parts, ofacrylonitrile are added dropwise at 65-70" C. The solution is thenstirred for about 15 hours at 6570 C. The benzene is then evaporated invacuo. The acrylonitrile combines additively completely with thecondensation product with the formation of a wax-like mass whichdissolves to a clear solution in dilute warm acetic acid. 1

10 parts'of the addition product so obtained are melted ona boilingwater bath and mixed with 34 parts of hot acetic acidof 6.2 percentstrength, while vigorously stirring. There is obtained a fine yellowishbrown paste which can be diluted with water.

165 parts of the addition product obtained as described in the firstparagraph of this example are melted and stirred 'at 100 C. with 32.5parts of freshly distilled benzyl chloride until a test portion iswater-soluble. The excess of 'benzyl chloride-is then removed in vacuo,and 600 parts of water at 70-80 C. are added to the 'melt while stirringwell. The mass is further stirred until a homogeneous paste is obtained.

165 parts of the addition product obtained as described in the firstparagraph of this example are melted, and 32.5 parts of neutral dimethylsulfate are added dropwise at 95-100 C. After stirring for a short time,600 parts of water at 60-70 C. are added while stirring well. There isobtained a paste which can be diluted with water while warming.

Example 11 A yarn of polyacrylonitrile fibers is treated for 30 minutesat 30-40 C. and at a liquor ratio of 1:30 in an aqueous bath in whichhas been dissolved a paste obtainable as described in any one ofExamples 1-10 or 13-15 in a proportion amounting to 0.4 to 1 percentcalculated on the weight of the yarn. After being dried the yarn has asoft feel.

Example 12 Viscose rayon is treated for 30 minutes and 20-30 C. and at aliquor ratio of 1:30 in a bath which contains 0.1-1 percent of thecondensation product obtainable as described in Examples 1-10 or 13-15.The rayon is then dried at 80 C. A viscose rayon with a soft feel isobtained.

Instead of to the viscose rayon fiber, a soft feel can be given to thefollowing fibers: cotton, linen, acetate rayon, Bemberg silk, polyesterfibers, for example to such as are made from polyethylene terephthalate,and fibers from polyamides and the various forms in which they areworked up.

Example 13 Operations are carried out as described in Example but,instead of using 10 parts of acrylonitrile, a warm benzene solution, inwhich 13.4 parts of acrylic acid amide are dissolved, is used.

A pale yellow wax-like product is obtained which is soluble in dilutewarm acetic acid and which, according to the process of Example 10, canbe converted into an acetic acid paste or into a paste which containsthe reaction product with benzyl chloride.

Example 14 Operations are carried out as described in Example 10 but,instead of using 10 parts of acrylonitrile, 16.9 parts offi-chloro-propionitrile are used. There is obtained the water-solublehydrochloride of the wax-like addition product of Example 10.

Example 15 A solution of 28.3 parts of diethylene triamine and 16.75parts of methacrylonitrile mol), containing 0.1 percent of hydroquinone,is heated for 72 hours at 80-85 C. while stirring. Under these workingconditions the methacrylonitrile additively combines completely with thediethylene triamine,.

140 parts of commercial stearic acid are then added, and the whole isheated in vacuo at 160-165 C. while stirring depending on the amount offoaming. After heating the mixture for 2-3 hours a test portion of thesubstance dissolves to a clear solution in dilute acetic acid.

10 parts of the above melt are mixed on a boiling water bath with 2parts of glacial acetic acid, whereupon, while stirring and adding 38parts of hot water, a slightly yellowish paste is obtained which can bediluted with more water to a clear solution.

What is claimed is:

I. As a new chemical compound a member selected from the groupconsisting of condensation products from one molecular proportion of apolyalkylene polyamine which is free from other substituents apart fromthe hydrocarbon radicals and the basic nitrogen atoms, 2 to 3 molecularproportions of an aliphatic monocarboxylic acid having a hydrocarbonradical of 12 to 18 carbon atoms and 1 to 2 molecular proportions of amember selected from the group consisting of acrylonitrile,rnethacrylonitrile, acrylic acid amides, methacrylic acid amides andp-chloro-propionic acid nitrile; and watersoluble salts of saidcondensation products.

2. As a new chemical compound a member selected from the groupconsisting of condensation products from one molecular proportion of apolyalkylene polyamine which is free from other substituents apart fromthe hydrocarbon radicals and the basic nitrogen atoms, 2 to 3 molecularproportions of an aliphatic monocarboxylic acid with a hydrocarbonradical of 12-18 carbon atoms and 1 to 2 molecular proportions ofacrylonitrile; and water-soluble salts of said condensation products.

3. As a new chemical compound the condensation product from onemolecular proportion of diethylene triamine, two molecular proportionsof stearic acid and 1 molecular proportion of acrylonitrile.

4. As a new chemical compound the acetate of the condensation productfrom one molecular proportion of diethylene triamine, two molecularproportions of stearic acid and 1 molecular proportion of acrylonitrile.

5. As a new chemical compound the benzyi chloride addition product ofthe condensation product from one molecular proportion of diethylenetriamine, two molecular proportions of stearic acid and 1 molecularproportion of acrylonitrile.

6. An organic fibrous textile material of enhanced soft feeling whichhas incorporated in it a member selected from the group consisting ofcondensation products from one molecular proportion of a polyalkylenepoly-amine which is free from other substitueuts apart from thehydrocarbon radicals and the basic nitrogen atoms, 2 to 3 molecularproportions of an aliphatic monocarboxylic acid having a hydrocarbonradical of 12 to 18 carbon atoms and 1 to 2 molecular proportions of amember selected from the group consisting of acrylonitrile,methacrylonitrile, acrylic acid amides, methacrylic acid amides andfl-chloro-propionic acid nitrile; and watersoluble salts of saidcondensation products.

7. An organic fibrous textile material of enhanced soft feeling whichhas incorporated in it a member selected from the group consisting ofcondensation products from one molecular proportion of a polyalkylenepolyamine which is free from other substituents apart from thehydrocarbon radicals and the basic nitrogen atoms, 2 to 3 molecularproportions of an aliphatic monocarboxylic acid with a hydrocarbonradical of 12-18 carbon atoms and 1 to 2 molecular proportions ofacrylonitrile; and water-soluble salts of said condensation products.

8. An organic fibrous textile material of enhanced soft feeling whichhas incorporated in it the condensation product from one molecularproportion of diethylene triamine, two molecular proportions of stearicacid and one molecular proportion of acrylonitrile.

9. An organic fibrous textile material of enhanced soft feeling whichhas incorporated in it the acetate of the condensation product from onemolecular proportion of diethylene triamine, two molecular proportionsof stearic acid and one molecular proportion of acrylonitrile.

10. An organic fibrous textile material of enhanced soft feeling whichhas incorporated in it the benzyl chloride addition product of thecondensation product from one molecular proportion of diethylenetriamine, two molecular proportions of stearic acid and one molecularproportion of acrylonitrile.

.7 11. As a new chemical compound. the condensation product from onemolecular proportion of triethylene tetramine, two molecular proportionsof acrylonitrile and two molecular proportions of stearic acid.

8 14. An "organic fibrous textile material of enhanced soft feelingwhich has incorporated in it the condensation product from one molecularproportion of diethylene triamine, one molecular proportion ofmethacrylonitrile and 12. As a new chemical compound the condensation 5two molecular proportions of stearic acid.

product from one molecular proportion of diethylene triamine, onemolecular proportion of. methacrylonitrile and two molecular proportionsof stearic acid.

13. An organic fibrous textile material of enhanced soft feeling whichhas incorporated init the condensa- 10 tion product from one molecularproportion of triethylene tetramine, two molecular proportions ofacrylonitrile and two molecular proportions of stearic acid.

References Cited in the file of'this patent UNITED STATES PATENTS2,304,369 Morgan et a1. Dec. 8, 1941 2,459,062 Cook et a1. Jan. 11,19492,468,086 Latham er a1 Apr. 26, 1949

6. AN ORGANIC FIBROUS TEXTILE MATERIAL OF ENHANCED SOFT FEELING WHICHHAS INCORPORATED IN IT A MEMBER SELECTED FROM THE GROUP CONSISTING OFCONDENSATION PRODUCTS FROM ONE MOLECULAR PROPORTION OF A POLYALKYLENEPOLYAMINE WHICH IS FREE FROM OTHER SUBSTITUENTS APART FROM THEHYDROCARBON RADICALS AND THE BASIC NITROGEN ATOMS, 2 TO 3 MOLECULARPROPORTIONS OF AN ALIPHAATIC MONOCARBOXYLIC ACID HAVING A HYDROCARBONRADICALS OF 12 TO 18 CARBON ATOMS AND 1 TO 2 MOLECULAR PROPORTIONS OF AMEMBER SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE,METHACRYLONITRILE, ACRYLIC ACID AMIDES, METHACRYLIC ACID AMIDES ANDB-CHLORO-PROPIONIC ACID NITRILE; AND WATERSOLUBLE SALTS OF SAIDCONDENSATION PRODUCTS.